Novel Fragrance Compounds

ABSTRACT

A compound having the structure 
     
       
         
         
             
             
         
       
     
     wherein R is hydrogen or methyl, having a strong odour and for use as a perfumery ingredient.

This application is a divisional of US application 12/513,311 filed Jun.3, 2009, which is a 371 application of PCT/GB2007/003961 filed Oct. 18,2007, which is claims priority to GB application 0622037.0 filed Nov. 4,2006.

FIELD OF THE INVENTION

The invention relates to the discovery of novel fragrance compounds, andperfumes and perfumed products comprising the novel compounds.

BACKGROUND

A major area of interest in the fragrance industry is to find high odourimpact fragrance materials which can provide superior performance atlower concentrations giving cost savings and lower environmental impact.

Muguet (Lily of the Valley) is an important area in perfumery (M Boelensand H Wobben, Perfumer & Flavorist, 1980, 5 (6), 1-8) and the odour iscreated by a combination of fragrance ingredients, of which3-(3/4-alkylphenyl)propanals such as Bourgeonal™(3-(4-tert-butylphenyl)propanal, U.S. Pat. No. 2,976,321), Florhydral™(3-(3-isopropylphenyl)butanal, EP 368156), Lily aldehyde™(3-4-tert-butylphenyl)-2-methylpropanal, U.S. Pat. No. 2,875,131) andCyclamen aldehyde™ (3-(4-isopropylphenyl)-2-methylpropanal, U.S. Pat.No. 1,844,013) provide floral, green and in particular watery aspects.All of these materials are used in Muguet accords in high volumes togood effect.

The relationship between molecular structure and odour has intrigued andperplexed scientists for two and a half millennia since Democritus andEpicurus first postulated a causal relationship among philosophicalcircles in Athens. The ability to accurately and consistently predictthe odour of putative molecules from their molecular structure continuesto prove elusive. Recent developments (which led to the award of a NobelPrize) in molecular biology have now given an insight into the reasonsbehind this. Discovery of the gene family encoding for olfactoryreceptor proteins (L. B. Buck and R. Axel, Cell, 1991, 65, 175-187)paved the way for confirmation that the sense of smell is combinatorialin nature and uses an array of hundreds of different receptor types. (B.Malnic, J. Hirono, T. 125Sato and L. B. Buck, Cell, 1999, 96, 713-723)Some of the issues raised by this in terms of odorant design aredescribed by no less a figure than another Nobel Laureate E. J. Corey ina paper on the understanding of odorant-receptor interaction. (S. Hongand E. J. Corey, J. Amer. Chem. Soc., 2006, 128, 1346-1352). A review onthe subject shows that, far from making rational odorant design easier,this new understanding indicates that accurate and consistent predictionof odour properties will remain beyond our grasp for the foreseeablefuture. (C. S. Sell, Angew. Chem. Int. Edn., 2006, 45, 6254-6261)Furthermore, an essay on property prediction from molecular structure(M. Jansen and J. C. Schoen, Angew. Chem. Int. Edn., 2006, 45,3406-3412) suggests that, at an even deeper level, all chemicalproperties of a proposed structure are not accurately and consistentlypredictable.

In a study made by R Pelzer et al (R Pelzer, U Harder, A Krempel, HSommer, S Surburg and P Hoever in Recent Developments in Flavour &Fragrance Chemistry—Proceedings of the 3^(rd) International Haarmann &Reimer Symposium, Ed R Hopp and K Mori, VCH, 1993 pp 29-67), 181substances possessing different aspects of the Lily of the Valleyfragrance were investigated with the use of computer models. For thealdehydic materials, 41 in total, the generic fragment structure

was developed and it was stated, amongst other requirements, that “adouble bond at C-4 is particularly advantageous, and may also be part ofan aromatic system”.

There are a smaller number of aldehydic materials that are non-aromaticand possess Muguet-like odours but these tend to have alicyclicterpinoid-like structures such as Trimenal.

EP 1054053 A discloses non-aromatic aldehydes with the generic structureof:

where R═H or Me, the dotted line representing either a double or singlebond and n=0 (when dotted line represents a single bond) and 1 (when thedotted line represents a double bond). In the latter case, the materialwas described as having an aldehydic, flowery-lily of the valley, fattytype of odour with a Lily aldehyde™/Bourgeonal™ connotation but isdescribed as definitely more floral, more white flower than that of Lilyaldehyde™. This molecule also fits the Pelzer model in that unsaturationis present at the C-4 position.

3-(3-methylcyclohexyl)propanal is disclosed in “Sur l'additionradiculaire d'acide bromhydrique, sur quelques composés allyliquescycloniques en présence de peroxyde de diterbutyle. Réactions desubstitution sur les bromures”, J-M Pabiot and R Pallaud, C. R. Acad.Sc. (1971), 273(6), 475-7. However no odour properties are disclosed.

SUMMARY OF THE INVENTION

Surprisingly we have found that 3-(3-alkylcyclohexyl)propanals provide ahigher odour impact relative to the commercially available substituted3-(3/4-alkylphenyl)propanals. This result is unexpected, since it iscommonly known that Muguet (Lily of the Valley) odorants based onaldehydic functionality have defined structural requirements, inparticular, unsaturation in the six-membered ring.

Thus, in a first aspect, the invention provides a compound having thestructure

where R₁ is C₁ to C₅ alkyl and R₂ to R₅ are independently selected fromH and methyl, with the proviso that when R₂ to R₅ are each H then R₁ isnot methyl.

In a second aspect, the invention provides a perfume comprising thecompound of Formula 1 where R₁ is C₁ to C₅ alkyl, and R₂ to R₅ areindependently selected from H and methyl.

In a third aspect, the invention provides use of a compound of Formula 1where R₁ is C₁ to C₅ alkyl, and R₂ to R₅ are independently selected fromH and methyl, for use as a perfumery ingredient.

Such novel aldehyde compounds have been surprisingly found to have astrong and pleasant odour and are suitable for use as perfumeingredients, particularly in Muguet accords/fragrances.

Preferably R₁ is selected from isopropyl, tert-butyl, sec-butyl,iso-butyl, 2,2-dimethylpropyl.

Preferred materials are where at least one of R₂ and R₃ is H and atleast one of R₄ and R₅ is H. A particularly preferred compound is whereR₁ is tert-butyl and R₂ to R₅ are each H.

The odour properties of the aldehydes of the invention mean that analdehyde, (including corresponding acetals or Schiffs bases), or mixtureof aldehydes in accordance with the invention, may be used as such toimpart, strengthen or improve the odour of a wide variety of products,or may be used as a component of a perfume (or fragrance composition) tocontribute its odour character to the overall odour of such perfume.

For the purposes of this invention a perfume means a mixture offragrance materials, if desired mixed with or dissolved in a suitablesolvent or mixed with a solid substrate.

The quantities in which one or more aldehydes according to the inventioncan be used in perfumes may vary within wide limits and depend, interalia, on the nature and the quantity of the other components of theperfume in which the aldehyde is used and on the olfactive effectdesired. It is therefore only possible to specify wide limits, which,however, provide sufficient information for the specialist in the art tobe able to use an aldehyde according to the invention for his specificpurpose. Typically, a perfume comprises one or more aldehydes inaccordance with the invention in an olfactively effective amount. Inperfumes an amount of 0.01% by weight or more of an aldehyde accordingto the invention will generally have a clearly perceptible olfactiveeffect. Preferably the amount is from 0.1 to 80% by weight, morepreferably at least 1% by weight.

In a further aspect, the invention provides a perfumed productcomprising a novel compound or perfume disclosed herein.

Example of such products are: fabric washing powders, washing liquids,fabric softeners and other fabric care products; detergents andhousehold cleaning, scouring and disinfection products; air fresheners,room sprays and pomanders; soaps, bath and shower gels, shampoos, hairconditioners and other personal cleansing products; cosmetics such ascreams, ointments, toilet waters, pre-shave, aftershave, skin and otherlotions, talcum powers, body deodorants and antiperspirants, etc.

The amount of the aldehyde according to the invention present inproducts will generally be at least 10 ppm by weight, preferably atleast 100 ppm, more preferably at least 1000 ppm. However, levels of upto about 20% by weight may be used in particular cases, depending on theproduct to be perfumed.

It has also been surprisingly discovered that certain aldehydes inaccordance with the invention show good substantivity to hair and cloth,both wet and dry, and hence have good potential for use in fabrictreatment products and hair care products.

It has also been surprisingly discovered that aldehydes in accordancewith the invention have antibacterial and antimicrobial properties,rendering them particularly suitable for inclusion in products asdescribed above. In particular 3-(3-tert-butylcyclohexyl)propanal hasbeen found to have excellent activity against Staphylococcus aureus. Inaddition, isomers of this material (e.g.3-(3-isopropylcyclohexyl)butanal) have also been found to have excellentactivity against Staphylococcus aureus, and may have some use inantibacterial fragrance technology in some applications.

A further surprising property of certain aldehydes of the presentinvention is the ability to possess insect repellency properties. Inparticular it has been found that 3-(3-tert-butylcyclohexyl)propanal hasexcellent repellency properties against mosquitoes and ants.

A further surprising property of certain aldehydes of the presentinvention is the ability to act as a malodour counteractant. Inparticular, 2-methyl-3-(3-methylcyclohexyl)propanal,3-(3-methylcyclohexyl)propanal and 3-(3-tert-butylcyclohexyl)propanalwere found to be particularly good malodour counteractants, especiallyagainst bathroom malodour.

Preparation

The compounds according to the invention may be prepared according toprocedures known in the art. The 3-(3-alkylcyclohexyl)propanals may beprepared in two stages from the corresponding3-(3-alkylphenyl)propanals. Firstly, the phenyl ring may be hydrogenatedusing catalytic techniques typically used for hydrogenation ofsubstituted benzene (R L Augustine in Heterogeneous Catalysis for theSynthetic Chemist, 1996, Marcel Dekker Inc., New York, ISBN0-8247-9021-9, pp 403-437). This hydrogenation technique will typicallyalso hydrogenate the aldehyde function of 3-(3-alkylphenyl)propanals andthus the product produced will be 3-(3-alkylcyclohexyl)propan-1-ols.Therefore secondly, the resultant alcohols are typically oxidised backto the aldehyde using stoichiometric oxidants such as 1,1,1-Tris(acetyloxy)-1,1-dihydro-1,2-benziodoxol-2-(1H)-one (Dess-Martinperiodinane) or catalytic vapour phase dehydrogenation using catalystssuch as copper chromite at 200-250° C., under 30 mBar.

Alternatively the 3-(3-alkylcyclohexyl)propanals may be prepared inthree stages from the corresponding 3-(3-alkylphenyl)propanals viaacetalisation. Firstly, the aldehyde function is converted to an acetalby reaction with an alcohol or suitable diol according to proceduresknown in the art. A generic example of a resultant acetal from ethyleneglycol is

Secondly, the phenyl ring may be hydrogenated using catalytic techniquestypically used for hydrogenation of substituted benzene to yield theacetal of 3-(3-alkylcyclohexy)propanal Thirdly, the acetal is hydrolysedusing procedures known in the art (S Sen et al J. Org. Chem. 1997,62,6684-86) to obtain the target 3-(3-alkylcyclohexyl)propanal.

The 3-(3-alkylcyclohexyl)propanals according to the invention aregenerally obtained as mixtures of cis and trans isomers (R₁ and thepropanal side chain are on the same side or opposite side of thecyclohexyl ring respectively). This cis/trans ratio is dependent uponthe synthesis procedure used and more particularly, dependent upon thehydrogenation procedure. Generally, the odours of both isomers aredifferent and the isomers may be separated by procedures known in theart such as column chromatography, fractional distillation and gaschromatography. The isomers may be used separately as fragrancematerials or the isomer mixture obtained from the synthetic proceduremay be used as such, depending on which particular odour character ormixture of odour characters is preferred for a particular application.

Also, the 3-(3-alkylcyclohexyl)propanals according to the inventionexist in various stereoisomeric forms. They are obtained by thesynthetic procedures described above as racemic mixtures, which may beseparated into the various stereoisomers by procedures known in the art,particularly by gas chromatography using chiral columns. Therefore, theinvention provides the 3-(3-alkylcyclohexyl)propanals as cis/trans andstereoisomeric mixtures as well as the various cis and trans andstereoisomers separately and includes the use of these separate isomersas fragrance materials.

Other Fragrance Materials

Other fragrance materials which can be advantageously combined with oneor more aldehydes according to the invention in a perfume are, forexample, natural products such as extracts, essential oils, absolutes,resinoids, resins, concretes etc., but also synthetic materials such ashydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters,acetals, ketals, nitriles, etc., including saturated and unsaturatedcompounds, aliphatic, carbocyclic, and heterocyclic compounds.

Such fragrance materials are mentioned, for example, in S. Arctander,Perfume and Flavor Chemicals (Montclair, N.J., 1969), in S. Arctander,Perfume and Flavor Materials of Natural Origin (Elizabeth, N.J., 1960),“Flavor and Fragrance Materials—1991”\ Allured Publishing Co. Wheaton,Ill. USA and in H Surburg and J Panten, “Common Fragrance and FlavorMaterials”, Wiley-VCH, Weinheim, 2006 ISBN-13: 978-3-527-31315-0,ISBN-10: 3-527-31315-X.

Examples of fragrance materials which can be used in combination withone or more aldehydes according to the invention are: geraniol, geranylacetate, linalool, linalyl acetate, tetrahydrolinalool, citronellol,citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate,tetrahydromyrcenol, terpineol, terpinyl acetate, nopol, nopyl acetate,2-phenyl-ethanol, 2phenylethyl acetate, benzyl alcohol, benzyl acetate,benzyl salicylate, styrallyl acetate, benzyl benzoate, amyl salicylate,dimethylbenzyl-carbinyl acetate, trichloro-methylphenyl-carbinylacetate, p-tert-butylcyclohexyl acetate, isononyl acetate, vetiverylacetate, vetiverol, ahexylcinnamaldehyde,2-methyl-3-(p-tert-butylphenyl) propanal,2-methyl-3-(p-isopropylphenyl)propanal, 2-(p-tert-butylphenyl)-propanal,2,4-dimethyl-cyclohex-3-enylcarboxaldehyde, tricyclodecenyl acetate,tricyclodecenyl propionate,4-(4-hydroxy-4methylpentyl)-3-cyclohexenecarboxyaldehyde,4-(4-methyl-3-pentenyl)-3-cyclohexenecarboxaldehyde,4-acetoxy-3-pentyltetrahydropyran, 3-carboxymethyl-2-pentylcyclopentanone, 2-n-heptylcyclopentanone,3-methyl-2-pentyl-2-cyclopentenone, n-decanal, n-dodecanal, 9-decenol-1,phenoxyethyl isobutyrate, phenylacetaldehyde dimethylacetal,phenylacetaldehyde diethyl acetal, geranyl nitrile, citronellyl nitrile,cedryl acetate, 3isocamphylcyclohexanol, cedryl methyl ether,isolongifolanone, aubepine nitrile, anisic aldehyde, heliotropin,coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal,ionones, methylionones, isomethylionones, irones, cis-3-hexenol andesters thereof, indane musks, tetralin musks, isochroman musks,macrocyclic ketones, macrocyclic lactone musks, ethylene brassylate.

Solvents which can be used for perfumes which contain an aldehydeaccording to the invention are, for example: ethanol, isopropanol,diethyleneglycol mono ethyl ether, dipropylene glycol, diethylphthalate, triethyl citrate, isopropyl myristate, etc.

The invention will be further described, by way of illustration in thefollowing examples.

EXAMPLE 1 Preparation of 3-(3-methylcyclohexyl)propanal i)3-(3-methylcyclohexyl)propan-1-ol

5% Ru/Al₂O₃ (3 g, 5 wt %), (2E)-3-(3-methylphenyl)acrylic acid (60 g,0.37 mol) and acetic acid (300 mL) were charged into a 500 mL autoclavevessel. The mixture was vigorously stirred under a hydrogen atmosphere(40 bar) at 150° C., for 3 days. The catalyst was filtered and theproduct was dissolved in ethyl acetate (500 mL), washed with water (500mL) and brine (500 mL). The organic phase was dried over sodiumsulphate, filtered and evaporated to yield crude3-(3-methylcyclohexyl)propanoic acid (60 g, 0.35 mol, 95% yield) as acolourless oil.

LiAlH₄ (16 g, 0.42 mol, 1.2 eq) and diethyl ether (450 mL) were chargedinto a 2 L three-necked round-bottom flask equipped with a mechanicalstirrer and a reflux condenser and cooled at 0° C. The crude3-(3-methylcyclohexyl)propanoic acid (60 g, 0.35 mol) was dissolved indiethyl ether (400 mL) and added dropwise to the reaction flask. Thereaction mixture was then stirred for 3 h at ambient temperature. Theexcess of lithium aluminium hydride was hydrolyzed with saturatedaqueous sodium sulphate and the mixture filtered. THF (1 L) was added tothe residue and the suspension was heated to 35° C. for 1 h. Thesuspension was filtered and the combined organic layers were dried oversodium sulphate and evaporated to yield the crude product as an oil.Chromatography on a silica gel column with 8% EtOAc in hexane as elutionagent, followed by a bulb-to-bulb distillation (0.1 mBar, 140° C.) gavepure 3-(3-methylcyclohexyl)propan-1-ol (35 g, gc purity>98%; yield=61%).

Odour: aldehydic, watery, fatty, citrus, nitrile.

Analytical Data (Predominantly One Isomer):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.46-1.72 (m, 15H); 0.85 (d, 3H);3.57-3.64 (m, 2H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 22.93 (q, 1C); 26.29 (t, 1C);30.12 (t, 1C); 32.67 (d, 1C); 32.92 (t, 1C); 33.49 (t, 1C); 35.31 (t,1C); 37.49 (d, 1C); 42.28 (t, 1C); 63.38 (t, 1C).

MS: m/z (relative intensity): 156 (M⁺, <1), 138 (5), 123 (5), 110 (44),97 (46), 96 (27), 95 (100), 82 (52), 81 (42), 69 (15), 67 (23), 55 (84),41 (23).

ii) 3-(3-methylcyclohexyl)propanal

In a 2 L three-necked round-bottom flask equipped with a mechanicalstirrer and a reflux condenser were introduced a solution of3-(3-methylcyclohexyl)propan-1-ol (23.3 g, 0.15 mol) in dichloromethane(140 mL), a solution of potassium bromide (1.77 g, 15 mmol, 0.1 eq) inwater (25 mL) and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO, 300 mg,1.92 mmol, 0.01 eq). To this mixture was added 0.35M aqueous sodiumhypochlorite (594 mL). The mixture was stirred for 3 days at 35° C. thenextracted with dichloromethane (500 mL). The organic layer was washedwith water (300 mL), 1N HCl (300 mL) and brine (300 mL), dried oversodium sulphate and concentrated. The crude product was chromatographedon silica gel with 8% EtOAc in hexane as elution agent, followed by abulb-to-bulb distillation (0.01 mBar, 79° C.) to give pure3-(3-methylcyclohexyl)propanal (11.8 g, gc purity>98%; yield=51%).

Odour: aldehydic, fatty, nitrile.

Analytical Data (Predominantly One Isomer):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.45-1.75 (m, 12H); 0.84 (d, 3H);2.38-2.44 (m, 2H); 9.73 (t, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 22.81 (q, 1C); 26.08 (t, 1C);29.40 (t, 1C); 32.53 (d, 1C); 32.57 (t, 1C); 35.08 (t, 1C); 37.16 (d,1C); 41.48 (t, 1C); 41.86 (t, 1C); 203.03 (d, 1C).

MS: m/z (relative intensity): 154 (M⁺, <1), 136 (12), 121 (15), 110(28), 108 (39), 97 (27), 95 (100), 82 (72), 81 (39), 69 (19), 68 (20),67 (27), 55 (86), 41 (33).

EXAMPLE 2 Preparation of 3-(3-tert-butylcyclohexyl)propanal i)1-(1-bromoethyl)-3-tert-butylbenzene

A solution of 1-tert-butyl-3-ethylbenzene (90 g, 0.54 mol) in carbontetrachloride (600 mL) was charged into a 2 L three-necked round-bottomflask, equipped with a mechanical stirrer and a reflux condenser. Thereaction was stirred vigorously while N-bromosuccinimide (97.6 g, 0.54mol, 1 eq) was added, followed by benzoyl peroxide (0.8 g, 2.23 mmol,0.004 eq). The reaction mixture was then heated to mild reflux for 1 h.Once cooled, the mixture was filtered and the organic phase was washedsuccessively with water (2×300 mL), 10% Na₂SO₃ water solution (150 mL),water (2×300 mL) and a saturated NaHCO₃ water solution (100 mL), driedover magnesium sulphate and concentrated. Unreacted1-tert-butyl-3-ethylbenzene was removed by fractional distillation (8.2mBar, 79-80° C.) to leave 1-(1-bromoethyl)-3-tert-butylbenzene (132 g,gc purity>90%; yield=95%), which was used as such for the next step.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.38 (s, 9H); 2.10 (d, 3H); 5.27(q, 1H); 7.32-7.48 (m, 4H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 26.97 (q, 1C); 31.29 (q, 3C);34.70 (s, 1C); 50.25 (d, 1C); 123.79 (d, 1C); 123.81 (d, 1C); 125.41 (d,1C); 128.35 (d, 1C); 142.81 (s, 1C); 151.47 (s, 1C).

MS: m/z (relative intensity): (no M⁺), 227 (2), 225 (2), 161 (100), 145(14), 131 (10), 117 (19), 105 (12), 91 (18), 77 (10), 57 (65), 41 (20),39 (14).

ii) 1-tert-butyl-3-vinylbenzene

Potassium hydroxide (140.9 g, 2.51 mol, 1.9 eq),1-(1-bromoethyl)-3-tert-butylbenzene (347.12 g, 90.9% gc pure, 1.31 mol,1 eq) and 2-propanol (2.6 kg) were charged into a 5 L three-neckedround-bottom flask, equipped with a mechanical stirrer and a refluxcondenser. After stirring for 2 h at 60° C., the reaction mixture wascooled to ambient temperature and poured into ice (1.7 kg), and theproduct was extracted with pentane (1.5 L). The organic phase thusobtained was washed twice with water (750 mL portions) and a saturatedNaHCO₃ water solution (300 mL), dried over Magnesium sulphate andconcentrated. The crude product was chromatographed on a silica gelcolumn with hexane as elution agent to give the product as a colourlessoil (119.6 g, gc purity of 93%), which was stabilised with 0.3 g of BHT.Flash distillation using a Vigreux column (3.4 mBar, 60-64° C.) gave1-tert-butyl-3-vinylbenzene (105.3 g, gc purity>97%, yield=50%).

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.37 (q, 9H); 5.27 (d, 1H); 5.78(d, 1H); 6.77 (dd, 1H); 7.28-7.35 (m, 3H); 7.45 (s, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 31.31 (q, 3C); 34.62 (s, 1C);113.42 (t, 1C); 123.17 (d, 1C); 123.42 (d, 1C); 124.92 (d, 1C); 128.23(d, 1C); 137.22 (s, 1C); 137.35 (d, 1C); 151.30 (s, 1C).

MS: m/z (relative intensity): 160 (M⁺, 19), 145 (100), 128 (12), 117(56), 115 (19), 105 (17), 91 (16), 77 (10), 63 (6), 57 (7), 51 (8), 41(8), 39 (13).

iii) 3-(3-tert-butylphenyl)propanal

Acetylacetonatodicarbonylrhodium (I) (41 mg, 0.1 mol %) of1-tert-butyl-3-vinylbenzene (29 g, 0.16 mol) and a solution oftriphenylphosphite (261 mg, 0.99 mmol) in 88 g of toluene were added toa 250 mL autoclave vessel. The vigorously stirred reaction mixtureheated for 6 h under a pressure of syn gas (mixture of hydrogen andcarbon monoxide in a ratio 1:1—1 Bar), at 80° C. The crude reactionmixture was concentrated in vacuo and chromatographed on a silica gelcolumn with 3% MTBE in hexane as elution agent to give3-(3-tert-butylphenyl)propanal (24.5 g, gc purity>82%; yield=63%).

Odour: aldehydic, floral, rubber.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.35 (s, 9H); 2.81 (t, 2H); 2.96(t, 2H); 7.01-7.30 (m, 4H); 9.85 (d, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 28.32 (t, 1C); 31.29 (q, 3C);34.54 (s, 1C); 45.35 (t, 1C); 123.21 (d, 1C); 125.22 (d, 1C); 125.27 (d,1C); 128.22 (d, 1C); 139.87 (s, 1C); 151.41 (s, 1C); 201.57 (d, 1C).

MS: m/z (relative intensity): 190 (M⁺, 32), 175 (82), 172 (0.5), 157(4), 147 (12), 133 (21), 131 (100), 119 (11), 117 (12), 116 (11), 115(17), 105 (16), 91 (26), 77 (10), 65 (5), 57 (17), 41 (9).

iv) 2-[2-(3-tert-butylphenyl)ethyl]-1,3-dioxolane

Ethylene glycol (15 mL, 0.27 mol, 1.2 eq), paratoluene sulfonic acid(430 mg, 1% w/w) and cyclohexane (50 mL) were charged into a 1 Lthree-necked round-bottom flask, equipped with a dean and stark, areflux condenser and a mechanical stirrer. 3-(3-tert-butylphenyepropanal(50.6 g, gc purity of 85%, 0.22 mol) was added dropwise at ambienttemperature. After stirring for 2 h at reflux, the reaction mixture wascooled to ambient temperature and washed twice with water (50 mL),saturated aqueous NaHCO₃, dried over magnesium sulphate and concentratedto give 2-[2-(3-tert-butylphenyl)ethyl]-1,3-dioxolane in the form of apale yellow coloured oil (60 g, gc purity>84%; yield>95%). The materialwas used as such for the next step.

Odour: floral, aldehydic, muguet, linalool.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.33 (s, 9H); 2.03 (m, 2H); 2.75(m, 2H); 3.87-5.05 (m, 4H); 4.93 (t, 1H); 7.05 (m, 1H); 7.25 (m, 3H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 30.37 (t, 1C); 31.35 (q, 3C);34.56 (s, 1C); 35.64 (t, 1C); 64.91 (t, 2C); 103.91 (d, 1C); 122.79 (d,1C); 125.41 (d, 2C); 128.02 (d, 1C); 141.13 (s, 1C); 151.16 (s, 1C).

MS: m/z (relative intensity): 234 (M⁺, 7), 219 (1), 191 (3), 172 (17),157 (12), 148 (11), 147 (13), 133 (32), 131 (24), 117 (16), 115 (16),105 (13), 100 (40), 92 (43), 91 (22), 87 (41), 77 (6), 73 (100), 57(48), 45 (20).

v) 2-[2-(3-tert-butylcyclohexyl)ethyl]-1,3-dioxolane

5% Ru/Al₂O₃ (3 g, 5% w/w) were charged into a 100 mL autoclave vesselwith 2-[2-(3-tert-butylphenyl)ethyl]-1,3-dioxolane (60 g, gc purity of84%, 0.21 mol). The mixture was vigorously stirred under an hydrogenatmosphere (60 Bar) at 130° C. for 4 h. The reaction mixture wasfiltered, rinsed with cyclohexane and concentrated to give2-[2-(3-tert-butylcyclohexyl)ethyl]-1,3-dioxolane in the form of a paleyellow coloured oil (62.1 g, gc purity>87%; yield>99%). The material wasused as such for the next step.

Odour: floral, muguet, citrus, salicylate, minty.

Analytical Data (Predominantly One Isomer):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.50-1.80 (m, 14H); 0.79 (s, 9H);3.76-3.93 (m, 4H); 4.79 (t, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 26.63 (t, 1C); 27.30 (t, 1C);27.49 (q, 3C); 31.35 (t, 1C); 31.87 (t, 1C); 32.41 (s, 1C); 33.08 (t,1C); 34.27 (t, 1C); 38.03 (d, 1C); 47.91 (d, 1C); 64.76 (t, 2C); 104.91(d, 1C).

MS: m/z (relative intensity) 240 (M⁺, <1), 239 (1), 183 (1), 163 (3),121 (7), 95 (4), 81 (4), 79 (4), 73 (100), 67 (5), 57 (10), 45 (7), 41(8).

vi) 3-(3-tert-butylcyclohexyl)propanal

2-[2-(3-tert-butylcyclohexyl)ethyl]-1,3-dioxolane (62 g, 0.22 mol, gcpurity of 87%) and dichloromethane/acetone in a 4:1 ratio (3.7 L) werecharged into a 5 L three-necked round-bottom flask equipped with areflux condenser and a mechanical stirrer. Iron (III) chloridehexahydrate (212.3 g, 0.78 mol, 3.5 eq) was added to the reaction atambient temperature. The reaction mixture was then stirred at ambienttemperature for 4 h and subsequently quenched, at 5-10° C., with theaddition of a saturated aqueous NaHCO₃ (500 mL). The organic phase wasthen washed with brine (500 mL), dried over magnesium sulphate andconcentrated. The resulting crude product was distilled via a Vigreuxcolumn (0.5 mBar, 82-85° C.), to give colourless oil (34.7 g, gc purity79%). The oil was chromatographed on a silica gel column with 2% EtOAcin hexane as elution agent giving 3-(3-tert-butylcyclohexyl)propanal(17.8 g, gc purity>98%, ratio cis:trans 75:25; yield 40%).

Odour: aldehydic, floral, muguet, green.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.52-0.86 (m, 3H), 0.80 (s, 9H),0.82 (s, 9H), 0.84-1.79 (m, 21H), 2.34-2.42 (m, 2H), 2.43 (td, 2H,J=7.63, 1.83 Hz), 9.75 (t, 1H, J=1.95 Hz), 9.77 (t, 1H, J=1.83 Hz).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 21.36 (t, 1C), 23.70 (t, 1C),26.51 (t, 1C), 27.19 (q, 3C), 27.32 (q, 3C), 27.50 (t, 1C), 27.57 (t,1C), 29.62 (t, 1C), 29.72 (t, 1C), 30.84 (t, 1C), 32.25 (s, 1C), 32.44(s, 1C), 32.83 (t, 1C), 33.16 (d, 1C), 34.18 (t, 1C), 37.69 (d, 1C),41.37 (d, 1C), 41.58 (t, 1C), 42.61 (t, 1C), 47.84 (d, 1C), 203.00 (d,1C), 203.10 (d, 1C).

Pure CIS-Isomer:

Odour: aldehydic, floral, muguet, watery.

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.52-0.67 (m, H); 0.76-0.86 (m,2H); 0.82 (s, 9H); 0.94-1.02 (m, 1H); 1.12-1.25 (m, 2H); 1.47-1.57 (m,2H); 1.65-1.79 (m, 4H); 2.43 (td, 2H, J=7.63, 1.83 Hz); 9.75 (t, 1H,J=1.95 Hz).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 26.51 (t, 1C); 27.19 (q, 3C);27.50 (t, 1C); 29.72 (t, 1C); 32.44 (s, 1C); 32.83 (t, 1C); 34.18 (t,1C); 37.69 (d, 1C); 41.58 (t, 1C); 47.84 (d, 1C); 203.10 (d, 1C).

MS: m/z (relative intensity) (no M⁺), 163 (7), 152(3), 139 (29), 121(28), 109 (3), 107 (5), 95 (26), 81 (25), 79 (20), 69 (12), 67 (23), 57(100), 41 (41).

Pure TRANS-Isomer:

Odour: aldehydic, floral, metallic.

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.80 (s, 9H); 0.84-0.96 (m, 1H);1.05-1.21 m, (2H); 1.30-1.43 (m, 2H); 1.43-1.55 (m, 2H); 1.55-1.63 (m,1H); 1.64-1.79 (m, 4H); 2.34-2.42 (m, 2H); 9.77 (t, 1H, J=1.83 Hz).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 21.36 (t, 1C); 23.70 (t, 1C);27.32 (q, 3C); 27.57 (t, 1C); 29.62 (t, 1C); 30.84 (t, 1C); 32.25 (s,1C); 33.16 (d, 1C); 41.37 (d, 1C); 42.61 (t, 1C); 203.00 (d, 1C).

MS: m/z (relative intensity) (no M⁺), 163 (4), 152 (6), 139 (34), 121(28), 109 (5), 107 (5), 95 (30), 81 (27), 79 (22), 69 (12), 67 (24), 57(100), 41 (45).

EXAMPLE 3 Preparation of 3-(3-methylcyclohexyl)butanal i)3-(3-methylphenyl)butanal

In a 1 L three-necked round-bottom flask equipped with a mechanicalstirrer and a reflux condenser were introduced DMF (300 mL), 3-bromotoluene (66.3 g, 0.39 mol), of crotyl alcohol (99 mL, 1.16 mol, 3 eq),sodium carbonate (102.5 g, 0.97 mol, 2.5 eq), tetrabutyl ammoniumbromide (107.6 g, 0.39 mol, 1 eq), palladium acetate (7.8 g, 11.6 mmol,3 mol %) and tri-o-tolyl phosphine (11.8 g, 38.7 mmol, 0.1 eq). Afterstirring for 1 h at 100-105° C., the reaction mixture was cooled toambient temperature. The reaction mixture was filtered over celite. Theorganic phase thus obtained was diluted with MTBE (800 mL) and washedthree times with water (500 mL portions), dried over magnesium sulphateand concentrated. The resulting crude product was fractionally distilledwith a Vigreux column (1 mBar, 70-81° C.) to give a colourless oil (39.6g, gc purity 90%). The oil was chromatographed on a silica gel columnwith 7% EtOAc in hexane as elution agent giving3-(3-methylphenyl)butanal (12.5 g, gc purity>99%; yield 36%).

Odour: green, watery/marine, aldehydic, marenil.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.31 (d, 3H); 2.34 (s, 3H); 2.70(m, 2H); 3.32 (m, 1H); 7.00-7.23 (m, 4H); 9.70 (t, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 21.42 (q, 1C); 22.15 (q, 1C);34.21 (d, 1C); 51.68 (t, 1C); 123.69 (d, 1C); 127.24 (d, 1C); 127.52 (d,1C); 128.53 (d, 1C); 138.21 (s, 1C); 145.38 (s, 1C); 201.96 (d, 1C).

MS: m/z (relative intensity) 162 (M⁺, 71), 147 (33), 144 (13), 133 (8),129 (14), 119 (100), 117 (37), 105 (76), 91 (61), 77 (21), 65 (16), 51(9), 41 (13), 39 (13).

ii) 3-(3-methylcyclohexyl)butan-1-ol

5% Ru/Al₂O₃ (500 mg, 5% w/w) was charged into a 25 mL autoclave vesselwith 3-(3-methylphenyl)butanal (10 g, 61.6 mmol). The mixture wasvigorously stirred under a hydrogen atmosphere (65 Bar) at 130° C. for5.5 h. The reaction mixture was filtered, rinsed with cyclohexane andconcentrated. The resulting crude product was distilled via abulb-to-bulb distillation (4.5 mBar, 125-130° C.) to give3-(3-methylcyclohexyl) butan-1-ol (8 g, gc purity>90%; yield 76%).

Odour: floral, muguet, green, lilac, terpineol.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.60-1.95 (m, 28H); 0.80-0.86 (m,12H); 0.82 3.56-3.70 (m, 4H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 16.06 (q, 2C); 22.99 (q, 1C);23.02 (q, 1C); 26.43 (t, 1C); 26.53 (t, 1C); 28.03 (t, 1C); 29.86 (t,1C); 32.91 (d, 1C); 33.00 (d, 1C); 34.38 (d, 1C); 34.43 (d, 1C); 35.43(t, 2C); 37.01 (t, 1C); 37.05 (t, 1C); 37.43 (t, 1C); 39.30 (t, 1C);42.65 (d, 2C); 61.52 (t, 2C).

MS: m/z (relative intensity) (no M⁺), 152 (3), 137 (2), 124 (57), 110(8), 97 (77), 96 (36), 95 (51), 81 (37), 69 (21), 67 (17), 55 (100), 41(28).

iii) 3-(3-methyl)cyclohexylbutanal

A solution of Dess Martin periodinane (17.4 g, 41 mmol, 1.1 eq) indichloromethane (250 mL) was charged into a 2 L three-neckedround-bottom flask, equipped with a mechanical stirrer and a refluxcondenser. 3-(3-methylcyclohexyl)butan-1-ol (6.4 g, 38 mmol) was addeddropwise, followed by a mixture of water (740 μL) in dichloromethane(740 mL) at ambient temperature over 1.5 h. After stirring for 2 h atambient temperature, the mixture was diluted with diethyl ether (200 mL)and washed with a 1:1 mixture of saturated aqueous NaHCO₃ and 10%Na₂S₂O₃ (2×100 mL) and brine (100 mL), dried over magnesium sulphate andconcentrated. The oil was chromatographed on a silica gel column with 7%EtOAc in hexane as elution agent giving 3-(3-methyl)cyclohexylbutanal(1.8 g, gc purity>80%; yield 28%).

Odour: aldehydic, green, muguet.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.54-0.83 (m, 4H); 0.83-0.91 (m,12H); 1.12-1.47 (m, 8H); 1.53-1.67 (m, 6H); 1.68-1.77 (m, 2H); 1.89-1.99(m, 2H); 2.13-2.22 (m, 2H); 2.40-2.48 (m, 2H); 9.73 (dd, 2H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 16.87 (q, 2C); 22.92 (q, 1C);22.93 (q, 1C); 26.25 (t, 1C); 26.32 (t, 1C); 28.57 (t, 1C); 29.68 (t,1C); 32.78 (d, 1C); 32.87 (d, 1C); 33.00 (d, 1C); 33.02 (d, 1C); 35.21(t, 2C); 37.91 (t, 1C); 39.01 (t, 1C); 42.55 (d, 1C); 42.56 (d, 1C);48.50 (t, 1C); 48.51 (t, 1C); 203.46 (d, 2C).

MS: m/z (relative intensity) 168 (M⁺, <1), 150 (2), 135 (11), 124 (75),109 (10), 97 (49), 95 (88), 81 (21), 71 (14), 69 (18), 68 (16), 67 (17),55 (100), 41 (33).

EXAMPLE 4 Preparation of 3-(3-isopropylcyclohexyl)butanal i)2-[2-(3-isopropylphenyl)propyl]-1,3-dioxolane

Ethylene glycol (18 mL, 0.32 mol, 1.2 eq), paratoluene sulfonic acid(400 mg, 1% w/w) and cyclohexane (50 mL) were charged into a 1 Lthree-necked round-bottom flask, equipped with a dean and stark, areflux condenser and a mechanical stirrer. Florhydral™3-(3-isopropylphenyl)butanal, 49.3 g, 0.26 mol) was added dropwise atambient temperature. The stirred mixture was then heated for 3 h atreflux. The reaction mixture was cooled at ambient temperature andwashed water (2×100 mL), dried over magnesium sulphate and concentrated.The resulting crude product was distilled with a Vigreux column (7.2mBar, 146° C.), to give 2-[2-(3-isopropylphenyepropyl]-1,3-dioxolane(239 g, gc purity>98%; yield 97%).

Odour: floral.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.25 (d, 6H, J=7.08 Hz); 1.30 (d,3H, J=7.08 Hz); 1.83-1.90 (m, 1H); 1.98-2.04 (m, 1H); 2.85-2.99 (m, 2H);3.76-3.84 (m, 2H); 3.92-3.99 (m, 2H); 4.70 (dd, 1H, J=6.35, 4.15 Hz);7.02-7.08 (m, 3H); 7.20-7.25 (m, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 22.63 (q, 1C); 24.03 (q, 2C);34.11 (d, 1C); 36.02 (d, 1C); 42.10 (t, 1C); 64.62 (t, 1C); 64.75 (t,1C); 103.35 (d, 1C); 124.02 (d, 1C); 124.21 (d, 1C); 125.25 (d, 1C);128.29 (d, 1C); 146.64 (s, 1C); 148.93 (s, 1C).

MS: m/z (relative intensity) 234 (M⁺, 1), 190 (1), 172 (7), 157 (7), 148(43), 133 (13), 131 (13), 117 (10), 115 (12), 105 (100), 100 (1), 99(20), 91 (22), 87 (46), 77 (8), 73 (93), 45 (22).

ii) 2-[2-(3-isopropylcyclohexyl)propyl]-1,3-dioxolane

5% Ru/Al₂O₃ (2 g, 5% w/w) was charged into a 100 mL autoclave vesselwith 2-[2-(3-isopropylphenyl)propyl]-1,3-dioxolane (40 g, 0.17 mol). Themixture was vigorously stirred under an hydrogen atmosphere (60-65 Bar)at 130° C. for 4 h. The reaction mixture was filtered, rinsed withcyclohexane and concentrated to give2-[2-(3-isopropylcyclohexyl)propyl]-1,3-dioxolane (126.5 g, gcpurity>98%; yield>99%) in the form of a colourless oil. The material wasused as such for the next step.

Odour: green, pyrazine, dusty, vetiver.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.72 (dd, 2H, J=16.24, 12.08 Hz);0.83 (d, 6H, J=6.84 Hz); 0.82 (d, 6H, J=6.84 Hz); 0.89 (d, 3H, J=6.84Hz); 0.88 (d, 3H, J=6.84 Hz); 0.92-1.82 (m, 26H); 3.78-3.85 (m, 4H);3.91-3.98 (m, 4H); 4.87 (dd, 2H, J=5.62, 4.64 Hz).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 16.21 (q, 1C); 16.42 (q, 1C);19.64 (q, 1C); 19.68 (q, 1C); 19.81 (q, 1C); 19.84 (q, 1C); 26.56 (t,1C); 26.65 (t, 1C); 28.24 (t, 1C); 29.72 (t, 1C); 29.76 (t, 1C); 29.99(t, 1C); 31.89 (t, 1C); 33.09 (d, 1C); 33.11 (d, 1C); 33.67 (t, 1C);34.35 (d, 1C); 34.41 (d, 1C); 38.12 (t, 1C); 38.43 (t, 1C); 43.06 (d,1C); 43.20 (d, 1C); 44.19 (d, 1C); 44.27 (d, 1C); 64.57 (t, 1C); 64.58(t, 1C); 64.74 (t, 1C); 64.74 (t, 1C); 104.20 (d, 1C); 104.24 (d, 1C).

MS: Major isomer: m/z (relative intensity) (no M⁺), 152 (2), 135 (1),109 (3), 95 (2), 82 (4), 73 (100), 69 (4), 67 (5), 55 (5), 45 (7), 41(6).

Minor isomer: m/z (relative intensity) (no M⁺), 152 (2), 135 (1), 109(3), 95 (2), 82 (4), 73 (100), 69 (4), 67 (5), 55 (5), 45 (7), 41 (7).

iii) 3-(3-isopropylcyclohexyl)butanal

2-[2-(3-isopropylcyclohexyl)propyl]-1,3-dioxolane (5 g, 20.8 mmol) and a4:1 mixture of dichloromethane:acetone (300 mL) were charged into a 3 Lthree-necked round-bottom flask equipped with a reflux condenser and amechanical stirrer. Iron (III) chloride hexahydrate (19.7 g, 72.8 mmol,3.5 eq) was added at ambient temperature. The reaction mixture was thenstirred at ambient temperature for 4 h and subsequently quenched at5-10° C. with the addition of saturated aqueous NaHCO₃ (500 mL). Theorganic phase was then washed with brine (500 mL), dried over magnesiumsulphate and concentrated. The resulting crude product was distilled viaa Vigreux column (1.3 mBar, 89° C.), to give3-(3-isopropylcyclohexyl)butanal (23.9 g, gc purity>91%; yield 62%).

Odour: green, violet, orris, aldehydic.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.65-0.76 (m, 2H); 0.78-0.94 (m,4H); 0.80-0.85 (m, 6H); 0.82 (d, 6H, J=6.84 Hz); 0.90 (d, 3H, J=7.08Hz); 0.89 (d, 3H, J=6.84 Hz); 0.97-1.10 (m, 2H); 1.12-1.28 (m, 4H);1.51-1.69 (m, 8H); 1.72-1.82 (m, 2H); 1.90-2.02 (m, 2H); 2.13-2.23 (m,2H); 2.42 (dd, 1H, J=4.88, 1.71 Hz); 2.46 (dd, 1H, J=4.88, 1.95 Hz);9.73 (dd, 2H, J=2.81, 2.08 Hz).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 16.74 (q, 1C); 17.03 (q, 1C);19.56 (q, 1C); 19.58 (q, 1C); 19.79 (q, 1C); 19.81 (q, 1C); 26.37 (t,1C); 26.45 (t, 1C); 28.84 (d, 1C); 29.46 (t, 1C); 29.51 (t, 1C); 29.96(t, 1C); 32.64 (t, 1C); 33.01 (d, 1C); 33.02 (d, 1C); 33.16 (d, 2C);33.66 (t, 1C); 42.73 (d, 1C); 42.83 (d, 1C); 44.01 (d, 1C); 44.10 (d,1C); 48.39 (t, 1C); 48.64 (t, 1C); 203.36 (d, 1C); 203.40 (d, 1C).

MS: m/z (relative intensity) (no M⁺), 178 (2), 163 (2), 152 (49), 135(24), 125 (9), 123 (13), 109 (74), 95 (13), 93 (12), 82 (100), 69 (77),67 (41), 55 (39), 41 (49).

EXAMPLE 5 Preparation of 3-(3-isopropylcyclohexyl)-2-methylbutanal i)3-(3-isopropylcyclohexyl)-2-methylenebutanal

A solution of 3-(3-isopropylcyclohexyl)butanal (6 g, 30.5 mmol) inisopropanol (3.5 mL) followed by formaldehyde (37% wt in water, 30.5mmol, 1 eq) was charged into a 50 mL three-necked round-bottom flaskequipped with a reflux condenser and a mechanical stirrer. Propionicacid (228 μL, 3.0 mmol, 0.1 eq) and pyrrolidine (255 μL, 3.0 mmol, 0.1eq) were added at ambient temperature. The reaction mixture was thenstirred at 45° C. for 3 h. The crude mixture was cooled to ambienttemperature dissolved in MTBE (100 mL) and washed with saturated aqueousNaHCO₃ (100 mL), brine (100 mL), dried over magnesium sulphate andconcentrated. The crude product was chromatographed on a silica gelcolumn with 3% EtOAc in hexane as elution agent giving3-(3-isopropylcyclohexyl)-2-methylenebutanal (5 g, gc purity>99%; yield78%).

Odour: woody, fruity, green, aldehydic.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.48-1.82 (m, 40H), 2.50-2.63 (m,2H), 5.98-6.03 (m, 2H), 6.17-6.22 (m, 2H), 9.48-9.53 (m, 2H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 15.87 (q, 1C), 16.08 (q, 1C),19.49 (q, 2C), 19.85 (q, 2C), 26.32 (t, 1C), 26.40 (t, 1C), 29.10 (t,1C), 29.27 (t, 1C), 29.29 (t, 1C), 31.28 (t, 1C), 32.77 (t, 1C), 32.99(d, 1C), 33.07 (d, 1C), 34.82 (t, 1C), 36.72 (d, 1C), 36.75 (d, 1C),41.40 (d, 1C), 41.62 (d, 1C), 43.88 (d, 1C), 44.00 (d, 1C), 133.97 (t,2C), 154.69 (s, 1C), 154.73 (s, 1C), 194.78 (d, 1C), 194.80 (d, 1C).

MS: Minor isomer: m/z (relative intensity) 208 (M⁺, 1), 193 (1), 165(3), 147 (7), 125 (62), 109 (5), 105 (4), 95 (5), 91 (6), 83 (47), 69(100), 55 (35), 41 (33).

Minor intensity m/z (relative intensity): 208 (M⁺, 1), 193 (1), 165 (2),147 (5), 125 (63), 109 (4), 105 (4), 95 (4), 91 (5), 83 (47), 69 (100),55 (33), 41 (31).

ii) 3-(3-isopropylcyclohexyl)-2-methylbutanal

5% Pd/C (250 mg, 5% w/w) was charged into a 25 mL autoclave vessel with3-(3-isopropylcyclohexyl)-2-methylenebutanal (4.5 g, 21.6 mmol) inmethanol (5 mL). The mixture was vigorously stirred under an hydrogenatmosphere (10 Bar) at 40-45° C. for 40 minutes. The catalyst wasfiltered over celite and the solution was concentrated. The resultingcrude product was distilled with a bulb-to-bulb distillation (2.5 mBar,117° C.) to give 3-(3-isopropylcyclohexyl)-2-methylbutanal (3 g, gcpurity>90%; yield=67%).

Odour: green, violet, apple, cucumber.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.57-0.79 (m, 2H), 0.79-0.93 (m,18H), 0.95 (dd, 2H, J=6.96, 2.81 Hz), 1.01-1.05 (m, 6H), 1.06-1.31 (m,4H), 1.31-1.46 (m, 5H), 1.46-1.70 (m, 8H), 1.70-1.86 (m, 3H), 2.27-2.56(m, 2H), 9.60-9.64 (m, 2H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 11.67 (q, 1C), 11.70 (q, 1C),13.95 (q, 1C), 14.05 (q, 1C), 19.51 (q, 1C), 19.62 (q, 1C), 19.80 (q,1C), 19.83 (q, 1C), 26.39 (t, 1C), 26.58 (t, 1C), 28.03 (t, 1C), 29.37(t, 1C), 29.52 (t, 1C), 31.73 (t, 1C), 31.80 (t, 1C), 33.00 (d, 1C),33.03 (d, 1C), 35.30 (t, 1C), 39.26 (d, 1C), 39.42 (d, 1C), 39.76 (d,1C), 39.77 (d, 1C), 44.01 (d, 1C), 44.30 (d, 1C), 49.69 (d, 1C), 49.82(d, 1C), 206.04 (d, 1C), 206.09 (d, 1C).

MS: Major isomer: m/z (relative intensity) 210 (M⁺, <1), 192 (1), 177(2), 152 (48), 149 (14), 123 (12), 109 (66), 97 (14), 95 (15), 82 (100),69 (82), 55 (47), 41 (49).

EXAMPLE 6 Preparation of 3-(3-tert-butylcyclohexyl)butanal i)3-(3-tert-butylphenyl)butanal

In a 1 L three-necked round-bottom flask equipped with a mechanicalstirrer and a reflux condenser were introduced DMF (200 mL),1-bromo-3-tert-butylbenzene (54.3 g, 0.25 mol), crotyl alcohol (65 mL,0.76 mol, 3 eq), sodium carbonate (66.2 g, 0.62 mol, 2.5 eq), tetrabutylammonium bromide (69.5 g, 0.25 mol, 1 eq), palladium acetate (5.05 g,7.5 mmol, 3 mol %) and tri-o-tolyl phosphine (7.6 g, 25 mmol, 0.1 eq).After stirring for 1 h at 90-100° C., the reaction mixture was cooled toambient temperature. The reaction mixture was filtered over celite. Theorganic phase thus obtained was diluted with MTBE (500 mL) and washedthree times with water (500 mL portions), dried over magnesium sulphateand concentrated. The resulting crude product was distilled with abulb-to-bulb distillation (3 mBar, 121° C.) to give a colourless oil(34.7 g, gc purity 73%). The crude product was chromatographed on asilica gel column with 5% EtOAc in hexane as elution agent giving3-(3-tert-butylphenyl)butanal (12.3 g, gc purity 99%; yield 39%).

Odour: floral, aldehydic, muguet, marine.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 1.33 (d, 3H, J=5.86 Hz); 1.32 (s,9H); 2.61-2.80 (m, 2H); 3.36 (qt, 1H, J=7.16, 6.96 Hz); 7.01-7.07 (m,1H); 7.23-7.27 (m, 3H); 9.72 (t, 1H, J=2.08 Hz).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 22.15 (q, 1C); 31.35 (q, 3C);34.53 (d, 1C); 34.66 (s, 1C); 51.83 (t, 1C); 123.49 (d, 1C); 123.55 (d,1C); 123.91 (d, 1C); 128.30 (d, 1C); 145.06 (s, 1C); 151.48 (s, 1C);202.04 (d, 1C).

MS: m/z (relative intensity) 204 (M⁺, 12), 189 (31), 171 (4), 161 (30),147 (100), 145 (81), 130 (17), 119 (24), 117 (23), 115 (21), 105 (25),91 (36), 77 (14), 65 (8), 57 (52), 41 (31).

ii) 3-(3-tert-butylcyclohexyl)butan-1-ol

5% Ru/Al₂O₃ (75 mg, 5% w/w) was charged into a 25 mL autoclave vesselwith 3-(3-tert-butylphenyl)butanal (1.5 g, 52 mmol). The mixture wasvigorously stirred under an hydrogen atmosphere (60-65 Bar) at 130° C.for 10 h. The reaction mixture was filtered, rinsed with cyclohexane andconcentrated. The resulting crude product was distilled with abulb-to-bulb distillation (0.5 mBar, 125-135° C.) to give3-(3-tert-butylcyclohexyl)butan-1-ol (1 g, gc purity>99%; yield 62%).

Odour: odourless.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.63-0.80 (m, 2H); 0.81-0.87 (m,6H); 0.83 (s, 18H); 0.87-1.88 (m, 26H); 3.54-3.80 (m, 4H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 15.91 (q, 1C); 16.35 (q, 1C);26.84 (t, 1C); 26.93 (t, 1C); 27.50 (t, 1C); 27.51 (t, 1C); 27.57 (q,3C); 27.58 (q, 3C); 28.08 (t, 1C); 29.72 (t, 1C); 29.93 (t, 1C); 31.57(t, 1C); 32.54 (s, 1C); 32.57 (s, 1C); 34.70 (d, 1C); 34.71 (d, 1C);36.85 (t, 1C); 37.40 (t, 1C); 43.08 (d, 1C); 43.31 (d, 1C); 48.27 (d,1C); 48.35 (d, 1C); 61.65 (t, 1C); 61.73 (t, 1C).

MS: Minor isomer: m/z (relative intensity) (no M⁺), 197 (1), 194 (2),179 (1), 166 (23), 155 (30), 137 (30), 123 (11), 110 (43), 109 (41), 95(62), 83 (35), 81 (94), 69 (44), 67 (48), 57 (100), 41 (56).

Major isomer: m/z (relative intensity) (no M⁺), 197 (1), 194 (2), 179(1), 166 (26), 155 (35), 137 (34), 123 (13), 110 (46), 109 (44), 95(64), 83 (36), 81 (97), 69 (45), 67 (49), 57 (100), 41 (56).

iii) 3-(3-tert-butylcyclohexyl)butanal

A solution of Dess Martin periodinane (1.8 g, 4.2 mmol, 1.1 eq) indichloromethane (30 mL) was charged into a 250 mL three-neckedround-bottom flask, equipped with a mechanical stirrer and a refluxcondenser. 3-(3-tert-butylcyclohexyl)butan-1-ol (805 mg, 3.79 mmol) wasadded dropwise, followed by a mixture of water (75 μL) indichloromethane (75 mL) at ambient temperature, over 1.5 h. Afterstirring for 2 h at ambient temperature, the mixture was diluted withdiethyl ether (100 mL) and washed with a 1:1 mixture of saturatedaqueous NaHCO₃ and 10% aqueous Na₂S₂O₃ (50 mL) and brine (50 mL). Theorganic phase was dried over magnesium sulphate and concentrated. Thecrude product was chromatographed on a silica gel column with 5% EtOAcin hexane as elution agent giving 3-(3-tert-butylcyclohexyl)butanal (100mg, gc purity>93%; yield 13%).

Odour: aldehydic, floral, herbal, watery.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.60-1.95 (m, 20H); 0.82 (s, 18H);0.89-0.92 (t, 6H); 1.93 (m, 2H); 2.15-2.47 (m, 4H); 9.74 (m, 2H).

13C NMR (101 MHz, CHLOROFORM-d) δ ppm: 16.67 (q, 1C); 17.19 (q, 1C);26.63 (t, 1C); 26.71 (t, 1C); 27.34 (t, 2C); 27.54 (q, 6C); 28.61 (t,1C); 29.75 (t, 1C); 30.34 (t, 1C); 31.33 (t, 1C); 32.54 (s, 1C); 32.55(s, 1C); 33.28 (d, 1C); 33.31 (d, 1C); 43.01 (d, 1C); 43.16 (d, 1C);48.11 (d, 1C); 48.18 (d, 1C); 48.33 (t, 1C); 48.78 (t, 1C); 203.44 (s,1C); 203.50 (s, 1C).

MS: Minor isomer: m/z (relative intensity): (no M⁺), 177 (4), 166 (19),135 (26), 121 (8), 109 (54), 95 (23), 93 (15), 81 (37), 79 (22), 67(42), 57 (76), 55 (38), 41 (100), 39 (49).

Major isomer: m/z (relative intensity): (no M⁺), 177 (4), 166 (19), 135(26), 121 (8), 109 (46), 95 (22), 93 (14), 81 (33), 79 (19), 67 (40), 57(68), 55 (31), 41 (100), 39 (45).

EXAMPLE 7 Preparation of 2-methyl-3-(3-methylcyclohexyl)propanal i)(2E)-2-methyl-3-(3-methylphenyl)acrylaldehyde

A solution of potassium hydroxide (24 g, 0.36 mol, 0.6 eq, with a purityof 85%) in ethylene glycol (120 g) and water (12 g) was charged into a500 mL three-necked round-bottom flask equipped with a reflux condenserand a mechanical stirrer. 3-methyl benzaldehyde (70 g, 0.59 mol) wasadded dropwise. The stirred reaction mixture was heated at 38-42° C. andpropionaldehyde (41 g, 0.71 mol, 1.2 eq) was dosed in over 3.25 h. Aftera further hour at 40° C., the reaction mixture was cooled to ambienttemperature and the two layers separated.

The organic layer thus obtained was washed with water (2×100 mL), driedover magnesium sulphate and concentrated. The resulting crude productwas distilled via a Vigreux column (1.0 mBar, 87-92° C.), to give(2E)-2-methyl-3-(3-methylphenyl)acrylaldehyde (65.9 g, gc purity>95%;yield 70%).

Odour: spicy, cinnamon.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 2.09 (d, 3H); 2.42 (s, 3H);7.20-7.38 (m, 5H); 9.59 (s, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 10.92 (q, 1C); 21.37 (q, 1C);127.08 (d, 1C); 128.54 (d, 1C); 130.33 (d, 1C); 130.70 (d, 1C); 135.05(s, 1C); 138.13 (s, 1C); 138.31 (s, 1C); 150.03 (d, 1C); 195.55 (d, 1C).

MS: m/z (relative intensity): 160 (M⁺, 25), 159 (22), 145 (100), 131(12), 128 (14), 117 (60), 115 (60), 105 (5), 91 (42), 77 (13), 65 (13),63 (14), 51 (14), 39 (25).

ii) 2-methyl-3-(3-methylcyclohexyl)propan-1-ol

5% Ru/Al₂O₃ (630 mg, 2.7% w/w) was charged into a 50 mL autoclave vesselwith (2E)-2-methyl-3-(3-methylphenyl)acrylaldehyde (23.5 g, 0.15 mol).The mixture was vigorously stirred under an hydrogen atmosphere (45-50Bar) at 160° C. for 7 h. The catalyst was filtered and the solution wasrinsed with cyclohexane and concentrated. The resulting crude productwas distilled via a Vigreux column (5 mBar, 102-104° C.) to give2-methyl-3-(3-methylcyclohexyl)propan-1-ol (13.7 g, gc purity>81%; yield60%).

Odour: floral, muguet, citrus.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.4-1.8 (m, 28H); 0.83-0.90 (m,12H); 3.32-3.35 (m, 4H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 16.84 (q, 1C); 16.845 (q, 1C);22.92 (q, 1C); 22.94 (q, 1C); 26.26 (t, 1C); 26.34 (t, 1C); 32.58 (d,1C); 32.60 (d, 1C); 32.62 (d, 1C); 32.72 (d, 1C); 33.84 (t, 2C); 34.79(d, 1C); 34.81 (d, 1C); 35.32 (t, 2C); 41.19 (t, 1C); 41.21 (t, 1C);41.96 (t, 1C); 43.16 (t, 1C); 68.73 (t, 1C); 68.74 (t, 1C).

MS: Major isomer: m/z (relative intensity) (no M⁺), 152 (7), 137 (7),123 (5), 110 (41), 97 (46), 95 (100), 82 (44), 81 (52), 69 (32), 67(24), 55 (97), 41 (34).

Minor isomer: m/z (relative intensity) (no M⁺), 152 (5), 137 (6), 123(5), 110 (39), 97 (35), 95 (100), 82 (43), 81 (53), 69 (29), 67 (24), 55(89), 41 (34).

iii) 2-methyl-3-(3-methylcyclohexyl)propanal

A solution of Dess Martin periodinane (4.1 g, 9.7 mmol, 1.1 eq) indichloromethane (43 mL) was charged into a 250 mL three-neckedround-bottom flask, equipped with a mechanical stirrer and a refluxcondenser. 2-methyl-3-(3-methylcyclohexyl)propan-1-ol (1.5 g, 8.8 mmol)was added dropwise, followed by a mixture of water (127 μL) indichloromethane (127 mL) at ambient temperature, over 1 h. Afterstirring for 1 h at ambient temperature, the mixture was diluted withdiethyl ether (100 mL) and washed with a 1:1 mixture of saturatedaqueous NaHCO₃ and 10% aqueous Na₂S₂O₃ (50 mL) and brine (50 mL), driedover magnesium sulphate and concentrated. The crude product waschromatographed on a silica gel column with 5% EtOAc in hexane aselution agent giving 2-methyl-3-(3-methylcyclohexyl)propanal (800 mg, gcpurity>90%; yield 54%).

Odour: floral, citrus, cuminic, nitrile.

Analytical Data (2 Isomers):

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.4-1.8 (m, 24H); 0.84 (d, 6H);1.04 (d, 6H); 2.30-2.60 (m, 2H); 9.56 (d, 2H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 13.74 (q, 1C); 13.76 (q, 1C);22.81 (q, 1C); 22.83 (q, 1C); 26.08 (t, 1C); 26.13 (q, 1C); 32.52 (d,2C); 32.57 (t, 1C); 33.22 (t, 1C); 34.99 (d, 1C); 35.02 (d, 1C); 35.12(t, 1C); 35.17 (t, 1C); 38.31 (t, 1C); 38.35 (t, 1C); 41.85 (t, 1C);42.49 (t, 1C); 43.72 (d, 1C); 43.74 (d, 1C); 205.58 (s, 2C).

MS: Major isomer: m/z (relative intensity) 168 (M⁺, 1), 150 (5), 135(10), 125 (6), 111 (68), 110 (58), 97 (26), 95 (63), 83 (17), 82 (22),81 (27), 69 (59), 67 (22), 58 (36), 55 (100), 41 (41).

Minor isomer: m/z (relative intensity) 168 (M⁺, <1), 150 (3), 135 (12),125 (5), 110 (60), 97 (22), 95 (75), 83 (15), 82 (26), 81 (32), 69 (63),67 (26), 58 (40), 55 (100), 41 (45).

EXAMPLE 8 Preparation of 2,2-dimethyl-3-(3-methylcyclohexyl)propanal i)2,2-dimethyl-3-(3-methylcyclohexyl)propan-1-ol

5% Rh/C (450 mg, 15% w/w) was charged into a 50 mL autoclave vesselcontaining a mixture of 2,2-dimethyl-3-(3-methylphenyl)propan-1-ol (6 g,34 mmol) in water (17 mL). The mixture was vigorously stirred under anhydrogen atmosphere (10 Bar) at 60° C. for 6 h. The reaction mixture wasfiltered and the filtrate was extracted with MTBE (25 mL), dried overmagnesium sulphate and concentrated. The resulting crude product wasdistilled with a bulb-to-bulb distillation (2.5 mBar, 90° C.) to give2,2-dimethyl-3-(3-methylcyclohexyl)propan-1-ol (5.1 g, gc purity>99%;yield 82%).

Odour: aldehydic, fatty/greasy, floral.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.51-0.88 (m, 2H), 0.79-0.87 (m,9H), 0.95-1.76 (m, 10H), 1.87 (br. s., 1H), 3.25 (s, 2H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 22.90 (q, 1C), 24.30 (q, 1C),24.31 (t, 1C), 26.53 (d, 1C), 32.90 (d, 1C), 33.58 (t, 1C), 34.83 (t,1C), 35.48 (t, 1C), 35.68 (s, 1C), 44.95 (t, 1C), 46.26 (t, 1C), 72.32(t, 1C).

MS: Major isomer: m/z (relative intensity) (no M⁺), 153 (34), 137 (3),111 (11), 97 (100), 83 (29), 69 (20), 55 (74), 41 (23).

Minor isomer m/z (relative intensity): (no M⁺), 153 (33), 137 (6), 111(11), 97 (100), 83 (30), 69 (23), 55 (79), 41 (25).

ii) 2,2-dimethyl-3-(3-methylcyclohexyl)propanal

A solution of Dess Martin periodinane (9.0 g, 21.1 mmol, 1.3 eq) indichloromethane (165 mL) was charged into a 250 mL three-neckedround-bottom flask, equipped with a mechanical stirrer and a refluxcondenser. The solution was cooled to 0° C. by the mean of an ice/saltbath. 2,2-dimethyl-3-(3-methylcyclohexyl)propan-1-ol (3.0 g, 16.3 mmol)was added dropwise. After stirring for 2 h at ambient temperature, themixture was cooled down to −15° C. and the solid was filtered off. Theorganic solution was then concentrated. The resultant crude product waschromatographed on a silica gel column with 2% EtOAc in hexane aselution agent giving 2,2-dimethyl-3-(3-methylcyclohexyl)propanal (1.0 g,gc purity>85%; yield 33%).

Odour: marine, watery.

Analytical Data:

¹H NMR (400 MHz, CHLOROFORM-d) δ ppm: 0.45-0.79 (m, 2H), 0.81 (d, 3H,J=6.59 Hz), 1.02 (s, 6H), 1.10-1.79 (m, 10H), 9.45 (t, 1H).

¹³C NMR (101 MHz, CHLOROFORM-d) δ ppm: 21.98 (q, 1C), 22.09 (q, 1C),22.81 (q, 1C), 26.22 (t, 1C), 32.66 (d, 1C), 34.13 (t, 1C), 34.20 (d,1C), 34.77 (t, 1C), 43.47 (t, 1C), 45.78 (t, 1C), 45.94 (s, 1C), 206.80(d, 1C).

MS: Major isomer: m/z (relative intensity) 182 (M⁺, <1), 164 (2), 153(15), 135 (2), 125 (4), 111 (21), 97 (100), 83 (28), 72 (94), 69 (30),55 (89), 41 (32).

EXAMPLE 9 Odour Intensity

3-(3-tert-butylcyclohexyl)propanal, hereafter referred to as Compound 1,was diluted in DPG to a level of 10 wt %. For comparison a 10 wt %solution in DPG of Florhydral™, and a neat Lily aldehyde™ compositionwere prepared.

The three compositions were added to a smelling strip and the odourintensity was assessed by a number of professional perfumers. All theperfumers indicated that the Compound 1 had a more intense odour thanthe Lily aldehyde™ and Florhydral™

EXAMPLE 10 Performance on Hair

Pantene™ shampoo was dosed at 0.2%—80 mg of ingredient was added to 40 gof Pantene™ shampoo base. Pantene™ shampoo dosed with 0.2% Lilyaldehyde™ was used as the standard (scale 0 to 10; Lily aldehyde™=5).Unperfumed Pantene™ was used for the control.

“Caucasian European” origin switches were used. Switches were wetted and10% by weight of the dry hair switch was added in product. The shampoowas massaged in to the hair switch for 30 s. The muguet odour intensity(foaming intensity) was then assessed. The switches were rinsed underhand hot warm water and towel dried. The muguet odour intensity (dampintensity) was then assessed. The hair switches were line dried for 3hours in an odour free room. The muguet odour intensity (dry intensity)was then assessed.

DRY DAMP FOAMING INTENSITY INTENSITY INTENSITY INGREDIENT MEAN RANGEMEAN RANGE MEAN RANGE LILY 5 — 5 — 5 — ALDEHYDE Compound 1 10% 8  7-10 8 7-10 9  7-10 DPG FLORHYDRAL 10% 4 2-7 6 4-8 5 4-6 DPG

Compound 1 outperformed Florhydral™ in Pantene™ shampoo. It showed verylinear performance on foaming, damp and dry hair and proved much moresubstantive on dry hair than any of the benchmarks.

EXAMPLE 11 Performance in Ariel™ High Suds (Handwash Powder)

Ariel™ high suds were dosed at 0.1%—20 mg of ingredient were added to 20g of powder. Ariel™ high suds dosed with 0.1% Lily aldehyde™ was used asthe standard. Unperfumed Ariel™ high suds was used for the control.

The bloom from bowl was assessed by dissolving 4.5 g of Ariel™ high sudsin 2 litres of tepid water, in a plastic bowl. Two terry towellingcloths were stirred in the solution for 5 minutes. The wash solution wasassessed (scale 0 to 10; Lily aldehyde™=5), giving the intensity frombowls figure. One cloth was rinsed in tepid water, hand wringed andodour assessed for rinsed cloth intensity (scale as above).

INTENSITY INTENSITY FROM BOWLS RINSED CLOTH INGREDIENT MEAN RANGE MEANRANGE LILY ALDEHYDE 5 — 5 — Compound 1 10% DPG 5 3-7 8 7-8 FLORHYDRAL10% DPG 3 2-4 4 2-6

Ariel™ high suds containing Compound 1 showed greater intensity thanFlorhydral™ Rinsed cloth with Ariel™ high suds containing Compound 1outperformed the benchmarks, indicating good substantivity on cloth.

EXAMPLE 12 Performance in Candle Wax

Candle wax house base (IGI hard paraffin wax mix) was dosed at1.0%—candles were left to mature at room temperature for 24 hours beforeassessment. All ingredients were used as 10% dilutions in benzylbenzoate. Intensity was assessed, by a panel of perfumers, from candleplaced in fragrance booths for one hour. All candles were firstevaluated in the cold wax before burning. Candles were then burned forone hour, in the fragrance booth, and odour assessed again for the burnmode intensity.

INGREDIENT COLD WAX MODE BURN MODE LILY ALDEHYDE 10% Faint odourcharacter, Not strong. Does not compare BENZYL BENZOATE no comparison toCompound 1. to the strength of Compound 1. COMPOUND 1 Very strong incold wax, excellent VERY strong, excellent performer 10% BENZYL BENZOATEstrength. for strength in burn mode. FLORHYDRAL 10% Not as strong asCompound 1. Still a Not as strong as Compound 1. BENZYL BENZOATE nicewatery floral note in cold wax. LYRAL 10% Faint odour character in coldmode. Very weak in burn. BENZYL BENZOATE

Compound 1 was much stronger than all of the benchmarks, both in coldwax and in burn mode.

EXAMPLE 13 Insect Repellency Results

Compound 1 was tested for insect repellency against mosquitoes and ants.In all cases, repellency is calculated with reference to an untreatedsurface having 0% repellency.

Tests results showed an excellent repellency against mosquitoes (100%repellency after 10 minutes, wrt untreated surface).

Compound 1 showed very good activity against ants (72% repellency overfirst hour, wrt untreated surface).

Protocols:

Ant test is completed with a simplified general purpose cleanerformulation:

Synperonic 91-6 5.0% Perfume.ingredient 1.0% Water 94.0%

This product is applied to the floor tiles (vinyl) at the rate of 20g·m⁻².

Ant (Lasius niger)300 mm square vinyl tiles half treated with 0.9 ml test material andleft for 2 hours.Glass arena 250 mm square, 75 mm high and fluon coated, open to air.Arena illuminated from 1.0 m above by four 18 W fluorescent lamps.50 black ants per arena counted every 5 minutes.Arena turned 180 degrees every 10 minutes.Any ants injured or escaping replaced.Mosquito (Aedes aegyptii)A perspex box approx 18 inch cube, with sleeved circular entry was usedas the test cage.The box contained 5 day old, mated honey fed females.The area of arm to be tested was measured.The test material was applied from ethanol solution at a rate of 0.2 mgtest material per square centimetre.A similar area of the other arm was used for the control.A pair of disposable gloves was worn on the hands throughout the test.In turn each arm was inserted into the cage for 30 seconds. This wasrepeated 3 times.The number of mosquitoes landing on the arm was recorded every fiveseconds.As penetration of the skin occurs within 5 seconds the arm was flickedat this frequency to dislodge the flies.

EXAMPLE 14 Antimicrobial Minimum Inhibitory Concentration (MIC)

One property that characterises the effectiveness of a compound orcomposition to inhibit the growth of bacteria, is the minimum inhibitoryconcentration, or MIC, of the compound or composition. The MIC isdefined as the minimum amount of a compound or composition (e.g. in ppm)at which little or no bacterial growth is observed. Generally, the lowerthe MIC of a compound or composition for a bacterium, the more effectivethe compound will be at inhibiting bacterial growth.

The minimum inhibitory concentration of a compound was determined by thefollowing method.

A culture of the test strains of bacteria Staphylococcus aureus ATCC6538 (American Type Culture Collection, P.O. Box 1549, Manassas, Va.20108, USA) was incubated for 16-24 hours, in a shaken flask at 37° C.The cultures was then diluted in sterile 0.1% TSB (Oxoid, Basingstoke,UK) to give a concentration of bacteria of approximately 10⁶ colonyforming units (cfu) per ml.

Fragrance compounds were prepared in sterile TSB to give stock solutionswith final concentrations of 40,000 ppm. The absorbance at 540 nm(hereinafter referred to for brevity and simplicity as “A₅₄₀”) was usedas a measure of turbidity resulting from bacterial growth. The MIC wastaken as the concentration of ingredient required to inhibit growth sothat the average change in absorbance during the incubation period was<0.2 A₅₄₀.

The results are shown below.

Material Known as MIC (ppm) 3-(3-tert-butylcyclohexyl)propanal Compound1 312 (156) 3-(3-isopropylcyclohexyl)butanal Compound 2 312 (156)2-methyl-3-(3-methylcyclohexyl)propanal Compound 3 50003-(3-methylcyclohexyl)propanal Compound 4 >5000

EXAMPLE 15 Malodour Counteracting

Fragrance materials were tested using small-scale tabletop method (3 mLmalodour in 15 mL jar+1 mL material oil in 15 mL jar both placed in 500mL jar (where either fragrance or malodour is tested alone DEP should beplaced in the other 15 mL jar). Bathroom malodour is used at 0.5%.

The perceived intensity of malodour and fragrance in each jar isassessed by a trained sensory panel using a line scale anchored at theextremes (0-100). The malodour control is used as a standard (perceivedintensity 75) against which all other perceived intensities are scaled.

A further jar was prepared as “hidden controls”, also containingmalodour only, but the panellists are unaware that it does not contain afragranced, or active, product.

Compounds 3 and 4 were tested for malodour counteracting performancewhen at 1% w/w in DPG. They significantly reduced the perceivedintensity of malodour and have similar performance as Cyprisate™ andCamonal™, which are well-known malodour counteractants.

EXAMPLE 16 Perfumed Products

A perfuming composition for a water based gel air freshener was preparedby admixing the following ingredients:

INGREDIENT % ADOXAL 0.2 AMYL SALICYLATE 3 ANISIC ALDEHYDE 0.5 ANTHER¹ 2BENZYL ACETATE 10 BENZYL SALICYLATE 4 CYCLAMEN ALDEHYDE 4 DIHYDROMYRCENOL 13.2 EFETAAL² 2 ELINTAAL³ 2 FLOROCYCLENE⁴ 5 FLOROSA⁵ 5HERBANATE⁶ 1 HEXYL SALICYLATE 4 INDOLE 0.1 JASMACYCLENE⁷ 5 JASMATONE⁸ 5LAVANDIN 5 LIGUSTRAL⁹ 1 LITSEA CUBEBA 1 METHYL DIHYDRO JASMONATE¹⁰ 2ORTHOLATE¹¹ 5 PELARGENE¹² 0.5 PHENYL ACETALDEHYDE DIMETHYL ACETAL 3PHENYL ACETIC ALDEHYDE 50% PEA 0.5 PHENYL ETHYL ACETATE 3.5 PHENYL ETHYLALCOHOL 5 SAGE DALMATIAN 0.5 SILVANONE¹³ 1 TERPINEOL 5 TOP ROSE AB¹⁴ 1TOTAL QUANTITY 100 ¹1-(2-((3-methylbutyl)oxy)ethyl)benzene; origin:Quest International, UK. ²1-(2-((1-(ethyloxy)ethyl)oxy)ethyl)benzene;origin: Quest International, UK.³3-((1-ethyloxy)ethyl)oxy)-3,7-dimethyl-1,6-octadiene; origin: QuestInternational, UK. ⁴3a,4,5,6,7,7a-hexahydro-4,7-methano-1H-inden-6-ylpropanoate; origin: Quest International, UK.⁵4-methyl-2-(2-methylpropyl)tetrahydro-2H-4-pyranol: QuestInternational, UK. ⁶ethyl3-isopropylbicyclo[2.2.1]hept-5-ene-2-carboxylate; origin: QuestInternational, UK. ⁷tricyclo[5.2.1.0 2,6]dec-4-en-8-yl ethanoate;origin: Quest International, UK. ⁸2-hexylcyclopentan-1-one; origin:Quest International, UK. ⁹cis and trans2,4-dimethyl-3-cyclohexene-1-carbaldehyde; origin: Quest International,UK. ¹⁰methyl 2-(3-oxo-2-pentylcyclopentyl)ethanoate; origin: QuestInternational, UK. ¹¹2-(1,1-dimethylethyl)cyclohexyl ethanoate; origin:Quest International, UK. ¹²3,6-dihydro-4,6-dimethyl-2-phenyl-2H-pyran;origin: Quest International, UK. ¹³mixture of oxacycloheptadecan-2-oneand cyclopentadecanone; origin: Quest International, UK. ¹⁴compoundedperfumery base; origin: Quest International, UK.

The addition of 0.25% of Compound 1 to the above-described perfumingcomposition, instead of an equivalent amount of Dihydro Myrcenol,enhanced the perceived odour intensity of the fragrance and impartedfreshness, white/floralcy to the composition.

A perfuming composition for a general purpose cleaner was prepared byadmixing the following ingredients:

INGREDIENT % 10%* ALLYL AMYL GLYCOLATE 0.2 BENZYL ACETATE 1 CIS 3HEXENOL 1 CIS 3 HEXENYL ACETATE 1 CYCLAMEN ALDEHYDE 2 DIHYDRO MYRCENOL 5DUPICAL¹ 0.3 EFETAAL² 2 ELINTAAL³ 3 FLOROSA⁴ 10 GERANYL ACETATE 5 INDOLE0.2 JASMATONE⁵ 3 LINALOL 26.3 MEFROSOL⁶ 20 METHYL DIHYDRO JASMONATE⁷ 2PHENYL ETHYL ALCOHOL 10 PHENYL PROPYL ALCOHOL 3 TETRAHYDRO GERANIOL 5TOTAL QUANTITY 100 *in dipropyleneglycol ¹4-tricyclo(5.2.1.02,6)dec-8-ylidenbutanal; origin: Quest International, UK.²1-(2-((1-(ethyloxy)ethyl)oxy)ethyl)benzene; origin: QuestInternational, UK.³3-((1-ethyloxy)ethyl)oxy)-3,7-dimethyl-1,6-octadiene; origin: QuestInternational, UK. ⁴4-methyl-2-(2-methylpropyl)tetrahydro-2H-4-pyranol:Quest International, UK. ⁵2-hexylcyclopentan-1-one; origin: QuestInternational, UK. ⁶3-methyl-5-phenylpentanol; origin: QuestInternational, UK. ⁷methyl 2-(3-oxo-2-pentylcyclopentyl)ethanoate;origin: Quest International, UK.

The addition of 0.50% of Compound 1 to the above-described perfumingcomposition, instead of an equivalent amount of Linalol, enhanced theperceived odour intensity of the fragrance and imparted freshness,white/floralcy to the composition.

1. A compound according to the formula (I)

wherein R is hydrogen or methyl.
 2. A compound according to claim 1wherein R is hydrogen.
 3. A compound according to claim 1 wherein R ismethyl.
 4. A method comprising using a compound according to the formula(I)

wherein R is hydrogen or methyl, as a perfume ingredient.